WO2019129809A1 - Matériau bionanohybride, son procédé de préparation et son utilisation - Google Patents

Matériau bionanohybride, son procédé de préparation et son utilisation Download PDF

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WO2019129809A1
WO2019129809A1 PCT/EP2018/097026 EP2018097026W WO2019129809A1 WO 2019129809 A1 WO2019129809 A1 WO 2019129809A1 EP 2018097026 W EP2018097026 W EP 2018097026W WO 2019129809 A1 WO2019129809 A1 WO 2019129809A1
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bionanohybrid
nanowires
enzyme
iron
process according
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José Miguel PALOMO CARMONA
Rocío BENAVENTE RUBIO
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Consejo Superior De Investigaciones Científicas (Csic)
Samsung Electronics Co., Ltd.
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Publication of WO2019129809A1 publication Critical patent/WO2019129809A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/96—Stabilising an enzyme by forming an adduct or a composition; Forming enzyme conjugates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer

Definitions

  • the invention relates to a high stable heterogeneous bionanohybrid material comprising protein and iron (II) carbonate nanowires (FeC03-NWs), process for the synthesis thereof and its use as a catalyst.
  • a high stable heterogeneous bionanohybrid material comprising protein and iron (II) carbonate nanowires (FeC03-NWs), process for the synthesis thereof and its use as a catalyst.
  • Iron is the most abundant metal in the planet, so being relative inexpensive, relatively nontoxic (considered by the regulatory authorities a “metal with minimum safety concern)(Medicines Agency, Guideline on the Specification Limits for Residues of Metal Catalysts or Metal Reagents, EMEA/ CHMP/SWP/4446/2000, London, February 21 , 2008) in comparison with other precious metals.
  • iron (Fe) is one of the mostly used metals for industrial applications.
  • Iron catalysis has gained an extraordinary attention in organic synthesis in the last years (Bauer, I., Knolker, H.J. Iron Catalysis in Organic Synthesis. Chem. Rev., 2015, 115, 3170) and the design and development of new kind of iron catalysts is highly desirable.
  • iron nanostructures have been strongly developed in the last years with different interesting properties (Nor, Y.A., Zhou, L., Meka, A.K., Xu, C., Niu, Y., Zhang, H., Mitter, N., Mahony, D., Yu, C. Engineering Iron Oxide Hollow Nanospheres to Enhance Antimicrobial Property: Understanding the Cytotoxic Origin in Organic Rich Environment. Adv. Func. Mat. 2016, 26, 5408; Gao, R., Zhang, H., Yan, D. Iron diselenide nanoplatelets: Stable and efficient water- electrolysis catalysts, Nano Energy, 2017 ,31, 90).
  • Magnetite (Fe304) nanoparticles are by far the most studied phase, and are applied in different areas, mainly with biomedical purpose (Arami, H., Khandhar, A., Liggitt, D., Krishnan, K. M. In vivo delivery, pharmacokinetics, biodistribution and toxicity of iron oxide nanoparticles. Chem. Soc. Rev. 2015,44, 8576).
  • iron nanostructures where depending on the metal source and experimental conditions the corresponding iron species and nanostructure is obtained.
  • the most typical iron species which can be obtained as nanoparticles are iron oxides hematite (a-Fe203), maghemite (y-Fe203), magnetite (Fe304), iron hydroxide (FeOOH) and in particular cases, a-Fe.
  • This last iron specie is quite difficult to obtain because of the extremely sensitivity of iron to oxidation under air conditions, exhibiting a core-oxide shell structure inevitably.
  • Fe and Fe oxides has been described to be synthesized mainly as nanoparticles with an average size from 10 to 100 mn.
  • Some process about the use of biomolecules (e.g. bacteria or plants) to synthesize of these nanoparticles has been described although in most of cases high size nanoparticles are obtained (Rufus, A., Sreeju, N., Philip, D. Synthesis of biogenic hematite (a-Fe203) nanoparticles for antibacterial and nanofluid applications. RSC Advances, 2016, 6, 94206).
  • magnetic nanowires offer potential advantages over magnetic nanoparticles because of their larger surface area to volume ratio and higher magnetic moments originated from their strong shape anisotropy.
  • Fe NWs has been successfully applied for example in comparison with other metal NWs with lower impact on cell viability (Martinez-Banderas, A.I., Aires, A., Teran, F.J., Perez, J.E., Cadenas, J.F., Alsharif, N., Ravasi, T., Cortajarena, A.L., Kosel, J. Functionalized magnetic nanowires for chemical and magneto-mechanical induction of cancer cell death, Scientific Reports, 2016, vol. 6).
  • Fe NWs, Fe203 or combination Fe/Fe203 or Fe/Fe304 nanowires were synthesized with an average diameter of 30 to 100 nm and length of 800 nm to 1 -2 pm as the best results in literature(Lupan, O., Postica, V., Wolff, N., Polonskyi, O., Duppel, V., Kaidas, V., Lazari, E., Ababii, N., Faupel, F., Kienle, L, Adelung, R.
  • Fe Nanowires has been used in catalytic process, for example in the degradation of organic molecules (Huang, Q., Cao, M., Ai, Z., Zhang, L. Reactive oxygen species dependent degradation pathway of 4-chlorophenol with Fe@Fe 2 0 3 core-shell nanowires. Applied Catalysis B: Environ, 2015 , 162, 319) or oxygen evolution reaction (OER) in U-0 2 batteries (Wang, F., Wu, X., Shen, C., Wen, Z. Facile synthesis of Fe@Fe203 core-shell nanowires as O2 electrode for high-energy U-O2 batteries, J. Solid State Electrochem., 2016, 20, 1831 ).
  • the present invention provides a new process to produce of protein-FeC03 nanowires bionanohybrid materials showing magnetic properties.
  • the bionanohybrids are efficient catalysts in the degradation of organic compounds.
  • the present invention discloses a protein-iron carbonate nanowires bionanohybrid material and the process for preparing thereof in aqueous media and in soft conditions.
  • the iron carbonate nanowires (FeC03 NWs) in the bionanohybrid material have an average diameter between 5 and 7 nm and average length of between 40 and 93 nm, showing magnetic properties and high catalytic capacity in the degradation of organic pollutants.
  • a first aspect of the present invention relates to a bionanohybrid material comprising:
  • FeC03 nanowires are embedded in the matrix.
  • the FeC03 nanowires are homogeneously distributed within the matrix.
  • the matrix is formed by the enzyme Candida antarctica lipase.
  • the FeC03 nanowires have an average length between 40 nm and 93 nm, and/or have an average diameter between 5 nm and 7 nm.
  • the FeC03 nanowires have an average diameter of 5 nm.
  • the FeC03 nanowires have an average diameter of 5 nm and an average length of 40 nm.
  • the FeC03 nanowires have an average length of 59 nm and/or an average diameter of 7 nm.
  • the bionanohybrid material having an average diameter of 5 nm is paramagnetic.
  • the interactions between the matrix and the FeC03 nanowires are non- covalent.
  • the bionanohybrid material has 47% by weight in Fe, obtained by elemental analysis ICP-OES (inductively coupled plasma optical emission spectrometry).
  • a second aspect of the present invention relates to a process for preparing protein-FeC03 nanowires bionanohybrid material.
  • the process comprises the next steps: a) addition under stirring of a protein or enzyme and of an iron (II) salt to an aqueous solution of sodium bicarbonate, wherein the pH of the aqueous solution of sodium bicarbonate is between the isoelectric point of the enzyme and 10, not including the isoelectric point of the enzyme, and wherein the isoelectric point of the protein or enzyme is below 10, b) incubation of the mixture obtained in step a) for a time between 14-16 h to obtain a bionanohybrid material (non-reduced bionanohybrid material).
  • Incubation means that the mixture is left under stirring for the specified time.
  • the bionanohybrid material obtained in step b) (also called in the present invention“non-reduced bionanohybrid material”), which is obtained in solid form in the suspension/mixture, is collected, washed with water and dried.
  • This bionanohybrid material comprises a matrix comprising an enzyme or protein and FeC03 nanowires embedded in the matrix, wherein the FeC03 nanowires have an average length of 59 nm and an average diameter of 7 nm.
  • the protein or enzyme induces the formation of nanowires.
  • the protein or enzyme allows the homogeneous distribution of the nanowires and avoids the formation of aggregates.
  • the process includes a step c) comprising the addition of sodium borohydride (reduction step) to the mixture obtained in step b) to form a bionanohybrid material (also called in the present invention “reduced bionanohybrid material”) in solid form, including smaller nanowires than the bionanohybrid material obtained in b), and collection of the solid formed in step c), washing with water and drying thereof.
  • a step c) comprising the addition of sodium borohydride (reduction step) to the mixture obtained in step b) to form a bionanohybrid material (also called in the present invention “reduced bionanohybrid material”) in solid form, including smaller nanowires than the bionanohybrid material obtained in b), and collection of the solid formed in step c), washing with water and drying thereof.
  • the combination of using a protein or enzyme for inducing the nanostructure formation and the use of sodium bicarbonate allows to synthesize for the first time iron (II) carbonate (siderite) nanowires.
  • the reducing step (addition of sodium borohydride) permits to achieve FeC03 NWs smaller than those obtained in step b) and showing magnetic properties.
  • the bionanohybrid material obtained in step c) comprises a matrix comprising an enzyme or protein and FeC03 nanowires embedded in the matrix, wherein the FeC03 nanowires have an average length between 40 nm and 93 nm and an average of 5 nm. More preferably, the bionanohybrid material obtained in step c) comprises FeC03 nanowires having an average diameter of 5 nm and an average length of 40 nm.
  • the bionanohybrid material obtained in step c) presents paramagnetic properties.
  • the pH of the aqueous solution of sodium bicarbonate in step a) must be above the isoelectric point of the enzyme and up to 10. Above pH 10, the synthesis of iron oxide nanoparticles is favored. The isoelectric point of the enzyme cannot be above 10.
  • the bionanohybrid material obtained in step b) or c) is collected, washed with water and dried.
  • the solution in step a) is stirring for avoiding iron oxidation.
  • the stirring is carried out at between 340-380 rpm, more preferably at 380 rpm.
  • the stirring speed is inferior to the above-mentioned range, the bionanohybrid material which is formed in solid form, would be deposited on the bottom so the bionanohybrid material would not be well-synthetized. On the contrary, if the stirring speed is higher than the above-mentioned range, oxidated side product would be formed.
  • step a) in step a) is added the enzyme Candida antarctica lipase.
  • the amount of enzyme or protein added in step a) is between 2.5 mg and 5 mg of enzyme or protein per 10 mL of the aqueous solution.
  • step a) is carried out at room temperature (20- 25 Q C) and under air.
  • step a) the addition of enzyme or protein is carried out at pH 10.
  • iron salt concentration ranges from 5 to 100 mg/ml in the aqueous solution; more preferably, 10 mg/ml.
  • the iron (II) salt is the sulfate of iron (II) and ammonium: (NH 4 ) 2 Fe(S04)2.
  • the time of the incubation (step b)) is 16 h.
  • step c) sodium borohydride is added to a final concentration of at least 0.12 M in the mixture, more preferably, between 0.12- 0.15 M.
  • step c) the mixture of reaction is preferably allowed to react between 15 and 360 min, more preferably 30 min and even more preferably 15 min.
  • the bionanohybrid material obtained in step b) or c) that has been collected, washed with water and dried is lyophilized.
  • it is lyophilized for a time between 16 and 18 h., more preferably 16 h.
  • the present invention also relates to a bionanohybrid material obtained by the process (in step b) or in step c)) described in the second aspect of the invention.
  • the bionanohybrid material obtained by the process of the invention has the features of the bionanohybrid material described in the first aspect of the present invention.
  • Another aspect of the present invention refers to the use of the bionanohybrid materials described in the present invention as catalysts.
  • bionanohybrid materials described in the present invention are used as catalysts for degrading organic pollutants, preferably phenolic compounds.
  • bionanohybrid materials both the reduced and the non- reduced bionanohybrid material
  • pAP 4-aminophenol
  • the reduced bionanohybrid material of the present invention is used for the reduction of 4-nitrophenol (pNP) to 4-aminophenol (pAP).
  • pNP contamination of surface and ground-water has gradually increased due to the excessive consumption of dyes, pesticides, and pharmaceuticals from industrial and agricultural activities.
  • United States Environmental Protection Agency set a guideline restricting the contaminant level of p-NP bellowing 10 ng/L in natural water.
  • pAP is the hydrolytic product of acetaminophen (paracetamol) and it has been reported to have significant nephrotoxicity and teratogenic effects.
  • nanowire in the present invention refers to an elongated nanostructure formed in a wire shape wherein the average length is between 40 to 93 nm and the average diameter is between 5 to 7 nm.
  • an aspect ratio (diameter: length) of the nanowires of the present invention ranges from.5:40 to 7:93.
  • bionanohybrid material in the present invention refers to a material comprising a protein or enzyme and wires with nanometric scale (“nanowires” as defined above).
  • embedded in the present invention when referring to the FeC03 nanowires means that FeC03 nanowires are disposed within the matrix, so they are surrounded by the matrix material.
  • this invention provides a simple and green technology to produce for the first time highly active, stable and reusable novel nanocatalysts; bionanohybrids constitute of very small iron carbonate nanowires in situ synthesized in a protein or enzyme matrix. These nanohybrids (nanohybrid material) present also magnetic properties, which permit a rapid recovering of the catalyst.
  • FIG. 1 X-ray diffraction (XDR) spectrum of the bionanohybrid material obtained in example 2 of the present invention.
  • FIG. 2 Transmission electron microscopy (TEM) images of FeC03 nanowires of bionanohybrid material obtained in example 2 of the present invention.
  • TEM Transmission electron microscopy
  • FIG. 3 Chemical scheme of the transformation of p-nitrophenol (pNP) into p- aminophenol (pAP).
  • FIG. 4 X-ray diffraction (XDR) spectrum of the bionanohybrid material CAL-B- FeC03NWs-15 obtained in example 2 of the present invention.
  • FIG. 5 TEM picture of the bionanohybrid material CAL-B-FeC03NWs-15 obtained in example 1 of the present invention.
  • FIG. 6 X-ray photoelectron spectroscopy (XPS) spectra of (a) Fe2p and (b) 01 s for iron carbonate in CAL-B-FeC03NWs-15 bionanohybrid obtained in example 1 of the present invention.
  • XPS X-ray photoelectron spectroscopy
  • FIG. 7 Reduction of pNP catalyzed by of the bionanohybrid CAL-B- FeCOsNWs-15 in aqueous media after 20 sg of reaction.
  • FIG. 8 Reduction of pNP catalyzed by others bionanohybrid (CAL-B- FeCO 3 NWs-30, CAL-B-FeC0 3 NWs-45, CAL-B-FeCO 3 NWs-60, CAL-B- FeCO 3 NWs-360) in aqueous media.
  • FIG. 9 Comparison of the XDR spectrum of CAL-B-FeC0 3 NWs bionanohybrid obtained in example 2 of the present invention from the preparation (day 1 ) to 30 days after.
  • FIG. 10 Comparison of the XDR spectrum of the bionanohybrid CAL-B- FeC03NWs-15 from the preparation (day 1 ) to 30 days after.
  • FIG. 11 TEM analysis of the bionanohybrids after 30 days’ store.
  • A) bionanohybrid material not treated with NaBH 4 (CAL-B-FeCOsNWs).
  • B) bionanohybrid material treated with NaBH 4 for 15 min (CAL-B-FeC03NWs-15).
  • Candida antartica B lipase (CAL-B) solution was from Novozymes (Denmark) (the concentration of the enzyme in the commercial solution is 5 mg /ml).
  • Ammonium iron (II) sulfate hexahydrate [(NH 4 )2Fe(S04)2 x 6H2O (Mohr ' s salt)], hydrogen peroxide (33%), sodium bicarbonate and sodium borohydride were purchased by Sigma-Aldrich.
  • Acetonitrile HPLC grade was purchased by Scharlab.
  • ICP-AES Inductively coupled plasma atomic emission spectrometry
  • XRD X-Ray diffraction
  • XPS X-ray photoelectron analysis
  • the reducing step with sodium borohydride was carried out for 15, 30, 60, 90 and 360 minutes to obtain the bionanohybrid materials: CAL-B-FeC03NWs-15, CAL-B-FeCO3NWs-30, CAL-B- FeCO3NWs-60, CAL-B-FeCOsNWs-90, CAL-B-FeCOsNWs-360, respectively.
  • the obtained mixture was centrifuged at 8000 rpm for 5 min, (11 ml_ per falcon type tube). The generated pellet was re-suspended in 15 mL of water. The pH of the supernatant solution was measured to be approximately 9.
  • Example 2 Synthesis bionanohvbrid material of the present invention without including the reduction step
  • Example 3 Catalytic Reduction of 4-nitrophenol (pNP) to 4-aminophenol (pAP) by the bionanohvbrid materials of the present invention
  • the fig. 3 shows the chemical scheme of the transformation of p-nitrophenol (pNP) into p-aminophenol (pAP).
  • This bionanohybrid material (CAL-B-FeC03NWs-15) showed the higher catalytic capacity to complete convert p-NP to p-AP within 20 seconds (3 mg catalyst, 2 ml, 1 mM pNP) ( Figure 7).
  • the CAL-B-FeCOsNWs-15 bionanohybrid was reused six cycles in the reduction of pNP using the conditions described above.
  • the catalyst was washed with water once and centrifuged before the next reaction.
  • the fresh catalyst was reused at least 6 reaction cycles in the reduction of pNP and more than 95% activity was conserved after that.
  • Example 6 Catalytic Degradation of p-aminophenol (pAP) by bionanohvbrid materials of the present invention
  • HPLC conditions were: an isocratic mixture of 30% acetonitrile and 70% bi-distilled water, UV detection at 275 nm and 225 nm using a Diode array detector, and a flow rate of 0.5 mL/min. Under these conditions, the retention times of pAP was 4.65 min, and for H2O2 was 3.3 min.
  • the reaction was quantitatively followed by HPLC.
  • the CAL-B-FeC03NWs-15 (obtained in example 1 ) and CAL-B-FeC03NWs (obtained in example 2) showed similar performance at these conditions and more than 98% degradation of pAP was achieved in 2 min (Table 2). No traces of any compounds were detected by HPLC after 50 min.
  • Example 7 Stability of the bionanohvbrid materials of the present invention
  • One important point for a possible industrial application of this protein-FeNWs bionanohybrids is the stability against oxidation.

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Abstract

La présente invention concerne la synthèse de bionanohybrides de nanofils fortement stables hétérogènes de protéine-carbonate de fer (II) (FeCO3-NW). Ils ont été préparés au moyen d'une enzyme dans une solution de bicarbonate aqueuse et de sel de fer (II) à la température ambiante et à l'air. L'enzyme induisait la formation in situ des NW de FeCO3 sur le réseau de protéines. L'addition de NaBH4 comme agent de réduction a permis d'obtenir des NW de FeCO3 ayant un diamètre d'environ 5 nm et une longueur d'environ 40 nm. Ces nouveaux bionanohybrides présentent une excellente stabilité à l'oxydation tout en conservant la capacité catalytique dans la dégradation des polluants organiques après 30 jours.
PCT/EP2018/097026 2017-12-28 2018-12-27 Matériau bionanohybride, son procédé de préparation et son utilisation WO2019129809A1 (fr)

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EP17382920.1A EP3505627A1 (fr) 2017-12-28 2017-12-28 Matériau bionanohybride, son procédé de préparation et son utilisation

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002093140A1 (fr) * 2001-05-14 2002-11-21 Johns Hopkins University Nanocables magnetiques multifonctionnels
WO2014132106A1 (fr) 2013-02-27 2014-09-04 University Of Calcutta Préparation et utilisation de nanoparticules métalliques
US8865116B2 (en) 2012-03-20 2014-10-21 Korea University Research And Business Foundation Method for preparation of hematite iron oxide with different nanostructures and hematite iron oxide prepared thereby

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002093140A1 (fr) * 2001-05-14 2002-11-21 Johns Hopkins University Nanocables magnetiques multifonctionnels
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